Method for producing fluorine-containing ether compounds

Abstract

Provided is a production method which makes it possible to produce a fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group with high yield while reducing the content of impurities.　The method for producing a fluorinated ether compound comprises: a step 1 for sulfonylating a fluorinated ether compound having a poly(oxyfluoroalkylene) chain and an alcohol group in the presence of a fluorine-based solvent, a base and a sulfonylating agent to produce a product containing a fluorinated ether compound having a poly(oxyfluoroalkylene) chain an a sulfonate group; and a step 2 for bringing the product produced in step 1 into contact with an adsorbent material having a pH value of 8.0 or less.

Description

[Technical Field]

[0001] The present invention relates to a method for producing a fluorinated ether compound. [Background technology]

[0002] Fluorine-containing ether compounds having a poly(oxyfluoroalkylene) chain and a reactive silyl group are suitable for use as surface treatment agents because they can form a surface layer on the surface of a substrate that exhibits high lubricity, water repellency, oil repellency, etc. When synthesizing the above-mentioned fluorine-containing ether compounds, it is known to use an intermediate obtained by reacting a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group with a sulfonylating agent such as trifluoromethanesulfonic anhydride (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-137509 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have investigated the procedure described in Patent Document 1 and found that the obtained product contains a large amount of impurities, and further improvement is required.

[0005] Therefore, an object of the present invention is to provide a method for producing a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group with a low impurity content and in high yield. [Means for solving the problem]

[0006] The inventors have found that the above problems can be solved by the following configuration. (1) Step 1, in the presence of a fluorine-containing solvent, a base, and a sulfonylating agent, to sulfonylate a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and an alcohol group, thereby obtaining a product containing a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group; A method for producing a fluorinated ether compound, comprising: a step 2 of contacting the product obtained in the step 1 with an adsorbent having a pH of 8.0 or less. (2) The method for producing a fluorinated ether compound according to (1), wherein the product obtained in step 1 is not subjected to a water washing treatment between the end of step 1 and the end of step 2. (3) Step 1, in the presence of a fluorine-containing solvent, a base, and a sulfonylating agent, to sulfonylate a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group, thereby obtaining a product containing a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group; step 3 of separating the product obtained in step 1 into two phases and separating and recovering the phase having a higher content of the fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group; and step 4 of contacting the separated and recovered phase with an adsorbent having a pH of 8.0 or less. (4) The method for producing a fluorinated ether compound according to (3), wherein the product obtained in step 1 is not subjected to a water washing treatment between the end of step 1 and the end of step 4. (5) The method for producing a fluorinated ether compound according to any one of (1) to (4), wherein the adsorbent has a pH of 7.0 or less. (6) The method for producing a fluorinated ether compound according to any one of (1) to (5), wherein the adsorbent has an average particle size of 1 to 500 μm. (7) The specific surface area of ​​the adsorbent is 30 to 900 m 2 The method for producing a fluorine-containing ether compound according to any one of (1) to (6), wherein the total amount of the fluorine-containing ether compound is 1 / g. (8) The method for producing a fluorinated ether compound according to any one of (1) to (7), wherein the water content of the adsorbent is 30% by mass or less. (9) The method for producing a fluorinated ether compound according to any one of (1) to (8), wherein the amount of the adsorbent used is 1 to 100 parts by mass per 100 parts by mass of the fluorinated ether compound having a poly(oxyfluoroalkylene) chain and an alcohol group. (10) The method for producing a fluorinated ether compound according to any one of (1) to (9), wherein the fluorinated ether compound having a poly(oxyfluoroalkylene) chain and an alcohol group is a compound represented by formula (1) described below. [Effects of the Invention]

[0007] According to the present invention, there can be provided a production method capable of producing a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group with a low impurity content and in high yield. DETAILED DESCRIPTION OF THE INVENTION

[0008] In this specification, a compound represented by formula (1) will be referred to as compound 1. Compounds represented by other formulas will be similarly described. A repeating unit represented by formula (I) will be referred to as unit I. Repeating units represented by other formulas will be similarly described. A group represented by formula (2) will be referred to as group 2. Groups represented by other formulas will be similarly described. As used herein, when it is stated that "the alkylene group may have an A group," the alkylene group may have an A group between carbon atoms in the alkylene group, or may have an A group at the terminal, such as alkylene group-A group-. In this specification, the "aryl group" in the "aryloxy group" includes not only aryl groups but also heteroaryl groups. In this specification, the term "linking group" refers not only to an aggregate of atoms, but also to an atom itself as long as it has the function of linking specific groups together. For example, a nitrogen atom itself is considered to be a trivalent linking group.

[0009] The terms used in the present invention have the following meanings. The "divalent organopolysiloxane residue" is a group represented by the following formula:x are each independently an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or a phenyl group. q is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

[0010] [ka]

[0011] The "number average molecular weight" of a compound is 1 H-NMR and 19 It is calculated by determining the number (average value) of oxyfluoroalkylene groups based on the number of terminal groups using F-NMR.

[0012] A first embodiment of the production method of the present invention includes Step 1 of sulfonylating a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group (hereinafter also referred to as "Specific Compound 1") in the presence of a fluorine-based solvent, a base, and a sulfonylating agent to obtain a product (hereinafter also referred to as "Specific Product") containing a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group (hereinafter also referred to as "Specific Compound 2"), and Step 2 of contacting the Specific Product with an adsorbent having a pH of 8.0 or less (hereinafter also referred to as "Specific Adsorbent"). It has been found that the above procedure allows the desired compound (specific compound 2) to be obtained in high yield with a low content of impurities. The present inventors have found that impurities can be efficiently removed without decomposing the specific compound 2 obtained in step 1 by contacting the specific product with a predetermined adsorbent. The procedure for each step will be described in detail below.

[0013] [Process 1] Step 1 is a step in which specific compound 1 is sulfonylated in the presence of a fluorine-based solvent, a base, and a sulfonylating agent to obtain specific compound 2. In the following, first, the materials used in step 1 will be described in detail, and then the procedure for step 1 will be described in detail.

[0014] <Fluorinated solvents> A fluorine-based solvent is a solvent containing a fluorine atom. Specific examples of the fluorine-based solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols. The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, for example, CF 13 H (AC-2000: product name, manufactured by AGC), C6F 13 Examples include C2H5 (AC-6000: product name, manufactured by AGC), and C2F5CHFCHFCF3 (Bertrel: product name, manufactured by DuPont). Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis(trifluoromethyl)benzene, and 1,4-bis(trifluoromethyl)benzene. The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, such as CF3CH2OCF2CF2H (AE-3000: product name, manufactured by AGC), C4F9OCH3 (Novec-7100: product name, manufactured by 3M), C4F9OC2H5 (Novec-7200: product name, manufactured by 3M), and C2F5CF(OCH3)C3F7 (Novec-7300: product name, manufactured by 3M). Specific examples of fluorinated alkylamines include perfluorotripropylamine and perfluorotributylamine. Specific examples of fluoroalcohols include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol. The fluorine-based solvents may be used alone or in combination of two or more kinds.

[0015] <base> The base may be an organic base or an inorganic base. Specific examples of the organic base include alkylamine compounds, arylamine compounds, allylamine compounds, and heterocyclic amine compounds, with alkylamine compounds and heterocyclic amine compounds being preferred from the viewpoint of superior versatility. A specific example of the alkylamine compound is triethylamine. Specific examples of heterocyclic amine compounds include pyridine, lutidine, collidine, pyrrole, pyrimidine, N,N-dimethyl-4-aminopyridine, 2,6-dimethylpyridine, and 2,6-di-tert-butylpyridine.

[0016] Specific examples of inorganic bases include alkali metal hydrides (sodium hydride, etc.), carbonates (sodium carbonate, potassium carbonate, cesium carbonate, etc.), hydrogen carbonates (sodium hydrogen carbonate, potassium hydrogen carbonate, etc.), alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), and alkali metal alkoxides (potassium tert-butoxide, etc.). The base may be used alone or in combination of two or more kinds.

[0017] <Sulfonylating agents> The sulfonylating agent refers to a compound capable of substituting a hydroxy group of a target compound with a sulfonate group. Examples of the sulfonylating agent include sulfonic acid halides and sulfonic acid anhydrides. Specific examples of sulfonic acid halides include p-toluenesulfonyl chloride, benzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, 2,4-dinitrobenzenesulfonyl chloride, and methanesulfonyl chloride. Specific examples of sulfonic acid anhydrides include trifluoromethanesulfonic acid anhydride, methanesulfonic acid anhydride, benzenesulfonic acid anhydride, p-toluenesulfonic acid anhydride, nitrobenzenesulfonic acid anhydride, chloromethanesulfonic acid anhydride, and trifluoroacetic acid anhydride.

[0018] <Specific compound 1> Specific Compound 1 is a compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group.

[0019] The poly(oxyfluoroalkylene) chain contains a plurality of units I shown below. (OX) Formula (I)

[0020] X is a fluoroalkylene group having one or more fluorine atoms. The fluoroalkylene group preferably has 1 to 6 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms. The fluoroalkylene group may be linear, branched or cyclic. The number of fluorine atoms in the fluoroalkylene group is preferably 1 to 2 times, and more preferably 1.7 to 2 times, the number of carbon atoms, in order to provide a film formed from a surface treatment agent produced using specific compound 2 with better abrasion resistance and water and oil repellency. The fluoroalkylene group is particularly preferably a group in which all hydrogen atoms in the fluoroalkylene group have been substituted with fluorine atoms (perfluoroalkylene group).

[0021] Specific examples of unit I include -OCHF-, -OCF2CHF-, -OCHFCF2-, -OCF2CH2-, -OCH2CF2-, -OCF2CF2CHF-, -OCHFCF2CF2-, -OCF2CF2CH2-, -OCH2CF2CF2-, -OCF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCH2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CH2-, -OCF2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CF2 2CF2CF2CH2-, -OCH2CF2CF2CF2CF2CF2-, -OCF2-, -OCF2CF2-, -OCF2CF2CF2-, -OCF(CF3)CF2-, -OCF2CF2CF2CF2-, - OCF(CF3)CF2CF2-, -OCF2CF2CF2CF2CF2-, -OCF2CF2CF2CF2CF2CF2-, -O-cycloC4F6-, -O-cycloC5F8-, -O-cycloC6F 10 - are some examples. Here, -cycloC4F6- means a perfluorocyclobutanediyl group, a specific example of which is perfluorocyclobutane-1,2-diyl, -cycloC5F8- means a perfluorocyclopentanediyl group, a specific example of which is perfluorocyclopentane-1,3-diyl, -cycloC6F 10 - means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0022] The repeat number m of the unit I contained in the poly(oxyfluoroalkylene) chain is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, still more preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.

[0023] The poly(oxyfluoroalkylene) chain may contain only one type of (OX), or may contain two or more types of (OX). The bonding order of two or more types of (OX) is not limited, and they may be arranged randomly, alternately, or in blocks. Containing two or more types of (OX) means that in specific compound 1, there are two or more types of (OX) with different numbers of carbon atoms, there are two or more types of (OX) with different numbers of hydrogen atoms, there are two or more types of (OX) with different positions of hydrogen atoms, and there are two or more types of (OX) with the same number of carbon atoms but different in the presence or absence of side chains or the type of side chain (the number of side chains, the number of carbon atoms in the side chain, etc.). For the arrangement of two or more (OX), for example, {(OCF2) m21 (OCF2CF2) m22 The structure represented by} indicates that m21 (OCF2) and m22 (OCF2CF2) are randomly arranged. m25 The structure represented by the formula indicates that m25 (OCF2CF2) and m25 (OCF2CF2CF2CF2) are alternately arranged.

[0024] (OX) represents a poly(oxyfluoroalkylene) chain m As for [(OCH ma F (2-ma) ) m11 ·(OC2H mb F (4-mb) ) m12 ·(OC3H mc F (6-mc) ) m13 ·(OC4H md F (8-md) ) m14 ·(OC5H me F (10-me) ) m15 ·(OC6H mf F (12-mf) ) m16 (O-cycloCH mg F (6-mg) ) m17 (O-cycloCH mh F (8-mh) ) m18 (O-cycloCH mi F (10-mi) ) m19 In this case, -cycloCH mg F (6-mg) represents a fluorocyclobutanediyl group, and preferably a fluorocyclobutane-1,2-diyl group. mh F (8-mh) represents a fluorocyclopentanediyl group, and preferably a fluorocyclopentane-1,3-diyl group. mi F (10-mi) represents a fluorocyclohexanediyl group, and is preferably a fluorocyclohexane-1,4-diyl group. ma is 0 or 1, mb is an integer from 0 to 3, mc is an integer from 0 to 5, md is an integer from 0 to 7, me is an integer from 0 to 9, mf is an integer from 0 to 11, mg is an integer from 0 to 5, mh is an integer from 0 to 7, and mi is an integer from 0 to 9. m11, m12, m13, m14, m15, m16, m17, m18 and m19 each independently represent an integer of 0 or more, and preferably 100 or less. m11+m12+m13+m14+m15+m16+m17+m18+m19 is an integer of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, still more preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50. Among these, m12 is preferably an integer of 2 or more, and an integer of 2 to 200 is particularly preferred. Also, C3H mc F (6-mc) , C4H md F (8-md) , C5H me F (10-me) and C6H mf F (12-mf) The alkyl group may be linear or branched, and is preferably linear.

[0025] In addition, m11 (OCH ma F (2-ma) ), m12 pieces (OC2H mb F (4-mb) ), m13 pieces (OC3H mc F (6-mc) ), m14 pieces (OC4H md F (8-md) ), m15 pieces (OC5H me F (10-me) ), m16 pieces (OC6H mf F (12-mf) ), m17 (O-cycloCH mg F (6-mg) ), m18 (O-cycloCH mh F (8-mh) ), m19 (O-cycloCH mi F (10-mi) ) may be joined in any order. If m11 is 2 or more, multiple (OCH ma F (2-ma) ) may be the same or different. If m12 is 2 or more, multiple (OC2H mb F (4-mb) ) may be the same or different. If m13 is 2 or more, multiple (OC3H mc F (6-mc) ) may be the same or different. If m14 is 2 or more, multiple (OC4H md F (8-md) ) may be the same or different. If m15 is 2 or more, multiple (OC5H me F (10-me) ) may be the same or different. If m16 is 2 or more, multiple (OC6H mf F (12-mf) ) may be the same or different. When m17 is 2 or more, multiple (O-cycloCH mg F (6-mg) ) may be the same or different. When m18 is 2 or more, multiple (O-cycloCH mh F (8-mh) ) may be the same or different. When m19 is 2 or more, multiple (O-cycloCH mi F (10-mi) ) may be the same or different.

[0026] (OX) m Preferably, has the following structure: {(OCF2) m21 (OCF2CF2) m22}, (OCF2CF2) m23 , (OCF(CF3)CF2) m23 , (OCF2CF2CF2) m24 , (OCF2CF2-OCF2CF2CF2CF2) m25 , {(OCF2CF2CF2CF2CF2) m26 (OCF2) m27}, {(OCF2CF2CF2CF2CF2) m26 (OCF2CF2) m27}, {(OCF2CF2CF2CF2CF2CF2) m26 (OCF2) m27}, {(OCF2CF2CF2CF2CF2CF2) m26 (OCF2CF2) m27}, (OCF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2-OCF2CF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2CF2) m28 , (OCF2-OCF2CF2CF2CF2CF2) m28 , (OCF2-OCF2CF2CF2CF2CF2CF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28 . Here, m21 is an integer of 1 or more, m22 is an integer of 1 or more, m21+m22 is an integer of 2 to 500, m23 and m24 are each independently an integer of 2 to 500, m25 is an integer of 1 to 250, m26 and m27 are each independently an integer of 1 or more, m26+m27 is an integer of 2 to 500, and m28 is an integer of 1 to 250.

[0027] (OX) m In terms of ease of production of Specific Compound 1, it is more preferable that the specific compound 1 has the following structure: {(OCF2) m21 (OCF2CF2) m22}, (OCF(CF3)CF2) m23 , (OCF2CF2CF2) m24 , (OCF2CF2)2{(OCF2) m21 (OCF2CF2) m22-2}, (OCF2CF2-OCF2CF2CF2CF2)m25-1 OCF2CF2, (OCF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2CF2CF2CF2CF2CF2-OCF2) m28 , (OCF2CF2-OCF2CF2CF2CF2CF2) m28-1 OCF2CF2, (OCF2CF2-OCF2CF2CF2CF2CF2CF2) m28-1 OCF2CF2. However, the numbers m22, m25 and m28 are selected so that m22-2, m25-1 and m28-1 are integers of 1 or greater. Among these, (OX) m is {(OCF2) m21 (OCF2CF2) m22} or (OCF2CF2-OCF2CF2CF2CF2) m25-1 Preferably it is OCF2CF2. {(OCF2) m21 (OCF2CF2) m22 In the formula}, m22 / m21 is preferably from 0.1 to 10, more preferably from 0.2 to 5.0, even more preferably from 0.2 to 2.0, particularly preferably from 0.2 to 1.5, and most preferably from 0.2 to 0.85.

[0028] (OX) m The number average molecular weight is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, and particularly preferably from 3,000 to 10,000. When the number average molecular weight is equal to or greater than the lower limit, the molecular chain of Specific Compound 1 becomes longer, thereby improving the flexibility of the molecular chain of Specific Compound 1. This further improves the adhesion between the substrate and the film formed by the surface treatment agent produced using Specific Compound 2. As a result, the abrasion resistance of the film becomes more excellent. In addition, the fluorine content of the film formed by the surface treatment agent produced using Specific Compound 2 is improved, resulting in more excellent water and oil repellency. Furthermore, if the number average molecular weight is equal to or less than the upper limit, the handling properties during film formation are better.

[0029] As the specific compound 1, the following compound 1 is preferred. A-(OX) m -OZ-(OH) g Formula (1)

[0030] A is a perfluoroalkyl group or -Q-(OH) k is. The perfluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The perfluoroalkyl group may be linear or branched.

[0031] Specific examples of perfluoroalkyl groups include CF3-, CF3CF2-, CF3CF2CF2-, CF3CF2CF2CF2-, CF3CF2CF2CF2CF2-, CF3CF2CF2CF2CF2CF2-, and CF3CF(CF3)-. The perfluoroalkyl group is preferably CF3-, CF3CF2-, or CF3CF2CF2-.

[0032] Q is a (k+1)-valent linking group, where k is an integer of 1 or more, and as described below, k is preferably an integer of 1 to 10. Therefore, Q is preferably a divalent to eleven-valent linking group. Q preferably has at least one branch point (hereinafter referred to as "branch point P") selected from the group consisting of C, N, Si, a ring structure, and a (k+1)-valent organopolysiloxane residue.

[0033] The ring structure is preferably one selected from the group consisting of a 3- to 8-membered aliphatic ring, a 3- to 8-membered aromatic ring, a 3- to 8-membered heterocycle, and a fused ring consisting of two or more of these rings, and the ring structures shown in the following formula are particularly preferred. The ring structure may have a substituent such as a halogen atom, an alkyl group (which may contain an ethereal oxygen atom between carbon atoms), a cycloalkyl group, an alkenyl group, an allyl group, an alkoxy group, or an oxo group (═O).

[0034] [ka]

[0035] Specific examples of the (k+1)-valent organopolysiloxane residue include the following groups. However, R in the following formula 5 are each independently a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 5 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0036] [ka]

[0037] Q is an alkylene group, a fluoroalkylene group, a hydroxyalkylene group, an alkoxyalkylene group, a carbonyl group, an amide bond, an ether bond, a thioether bond, a urea bond, a urethane bond, a carbonate bond, an ester bond, or -SO2NR 6 -, -Si(R 6 )2-, -OSi(R 6 )2-, -Si(CH3)2-Ph-Si(CH3)2-, and a group containing one or more selected from the group consisting of a divalent organopolysiloxane residue. However, R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and Ph is a phenylene group. 6 The number of carbon atoms in the alkyl group is preferably 1 to 3, and particularly preferably 1 or 2, in terms of ease of production of the specific compound 1. In addition, each bond or group constituting Q has a terminal A-(OX) m For example, an amide bond can be formed by placing the carbon atom at the A-(OX) m The nitrogen atom may be located on the -O side, and the nitrogen atom may be A-(OX) m It may be located on the -O side. The same applies to other bonds and groups.

[0038] Specific examples of the divalent organopolysiloxane residue include groups of the following formula: 7 are each independently a hydrogen atom, an alkyl group, an alkoxy group, or a phenyl group. 7 The alkyl group and alkoxy group preferably have 1 to 10 carbon atoms, and particularly preferably 1 carbon atom.

[0039] [ka]

[0040] Q is —C(O)NR 6 -, -C(O)-, -C(O)OR 6 -, -NR 6 It is also preferred that the group has at least one bond selected from the group consisting of - and -O-, and is -C(O)NR 6 It is particularly preferred to have -, -O- or -C(O)-.

[0041] Q may be a combination of two or more divalent hydrocarbon groups and one or more branching points P, or a combination of two or more hydrocarbon groups, one or more branching points P, and one or more bonds B. Specific examples of the divalent hydrocarbon group include divalent aliphatic hydrocarbon groups (such as alkylene groups and cycloalkylene groups) and divalent aromatic hydrocarbon groups (such as phenylene groups). The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0042] In compound 1, X has the same definition as X in unit I above, and m is an integer of 2 or more.

[0043] Z is a (g+1)-valent linking group. The definition of Z is the same as that of Q described above, except that the (k+1) valence in Q described above is replaced with (g+1) valence. In Specific Compound 1, Z and Q may be the same or different. From the standpoint of ease of production of Specific Compound 1, it is preferable that Z and Q are the same.

[0044] g is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 to 3. k is an integer of 1 or more, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0045] As Compound 1, Compound 1-11 and Compound 1-21 are preferred.

[0046] A-(OX) m -OY 11 -(OH) g1 Formula (1-11) (OH) k1 Y 22 -(OX) m -OY 21 -(OH) g2 Formula (1-21)

[0047] In formula (1-11), A, X, and m have the same definitions as A, X, and m in formula (1), respectively. Y 11 is a (g1+1)-valent linking group, and specific examples thereof are the same as Z in formula (1). g1 is an integer of 1 or more, preferably an integer of 1 to 4, and more preferably 1 to 3.

[0048] In formula (1-21), X and m have the same definitions as X and m in formula (1), respectively. k1 is an integer of 1 or more, preferably an integer of 1 to 4, and more preferably 1 to 3. Y 22 is a (k1+1)-valent linking group, and specific examples thereof are the same as Q in formula (1). Y 21 is a (g2+1)-valent linking group, and specific examples thereof are the same as Z in formula (1). g2 is an integer of 1 or more, preferably an integer of 1 to 4, and more preferably 1 to 3.

[0049] Y in formula (1-11) 11 may be a group g2-1 (where d1+d3=1 (i.e., d1 or d3 is 0), g1=d2+d4, d2+d4≧1), a group g2-2 (where e1=1, g1=e2, e2≧1), a group g2-3 (where g1=2), a group g2-4 (where h1=1, g1=h2, h2≧1), a group g2-5 (where i1=1, g1=i2, i2≧1), a group g2-6 (where g1=1), a group g2-7 (where g1=i3+1), a group g2-8 (where g1=i4, i4≧1), or a group g2-9 (where g1=i5, i5≧1). Also, Y in formula (1-21) 21 and Y 22 may each independently be a group g2-1 (where g2=d2+d4, k1=d2+d4), a group g2-2 (where g2=e2, k1=e2), a group g2-3 (where g2=2, k1=2), a group g2-4 (where g2=h2, k1=h2), a group g2-5 (where g2=i2, k1=i2), a group g2-6 (where g2=1, k1=1), a group g2-7 (where g2=i3+1, k1=i3+1), a group g2-8 (where g2=i4, k1=i4), or a group g2-9 (where g2=i5, k1=i5).

[0050] [ka]

[0051] (-A 1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -) e2 Formula (g2-2) -A 1 -N(-Q 23 -)2 formula (g2-3) (-A 1 -) h1 Z 1 (-Q 24 -) h2 Formula (g2-4) (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -) i2 Formula (g2-5) -A 1 -Q 26 - Formula (g2-6) -A 1 -CH(-Q 22 -)-Si(R e3 ) 3-i3 (-Q 25 -) i3 Formula (g2-7) -A 1 -[CH2C(R e4 )(-Q 27 -)] i4 -R e5 Formula (g2-8) -A 1 -Z a (-Q 28 -) i5 Formula (g2-9)

[0052] However, in formulas (g2-1) to (g2-9), A 1 (OX) m Connect to the Q side 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 connects to the OH side.

[0053] A 1 represents a single bond, an alkylene group, or an alkylene group with two or more carbon atoms that has -C(O)NR between carbon atoms. 6 -, -C(O)-, -OC(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-N(R 6)SO2- or C(O)NR at the end opposite to the A side of the alkylene group 6 -, -C(O)-, -OC(O)-, -OC(O)O-, -NHC(O)O-, -NHC(O)NR 6 -, -O-, -SO2NR 6 -or-N(R 6 ) SO2-, and in each formula, A 1 If there are two or more, there are two or more A 1 may be the same or different. A hydrogen atom of the alkylene group may be substituted with a fluorine atom. Q 11 represents a single bond, -O-, an alkylene group, or -C(O)NR between carbon atoms of an alkylene group having two or more carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-. Q 22 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, -C(O)NR at the end of the alkylene group not connected to OH 6 -, -C(O)-, -NR 6 A group having - or -O-, or an alkylene group having 2 or more carbon atoms having -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O- and -C(O)NR at the end not connected to OH 6 -, -C(O)-, -NR 6 - or -O-, and in each formula, Q 22 If there are two or more, there are two or more Q 22 may be the same or different. Q 23 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and two Q 23 may be the same or different. Q24 Q 24 Z binds to 1 If the atom in is a carbon atom, Q 22 and Q 24 Z binds to 1 If the atom in is a nitrogen atom, Q 23 In each formula, Q 24 If there are two or more, there are two or more Q 24 may be the same or different. Q 25 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and in each formula, Q 25 If there are two or more, there are two or more Q 25 may be the same or different. Q 26 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or a group having -O-. R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Q 27 is a single bond or an alkylene group. 27 If there are two or more, there are two or more Q 27 may be the same or different. Q 28 Q is an alkylene group or a group having an etheric oxygen atom or a divalent organopolysiloxane residue between carbon atoms in an alkylene group having two or more carbon atoms. 28 If there are two or more, there are two or more Q 28 may be the same or different.

[0054] Z 1 is A 1 has a carbon atom or nitrogen atom to which Q is directly bonded, 24 is a group having an h1+h2 valent ring structure having a carbon atom or nitrogen atom to which is directly bonded.

[0055] R e1 is a hydrogen atom or an alkyl group, and in each formula, R e1 If there are two or more, there are two or more R e1 may be the same or different. R e2 is a hydrogen atom, a hydroxyl group, an alkyl group, or an acyloxy group. e2 If there are two or more, there are two or more R e2 may be the same or different. R e3 is an alkyl group. e3 If there are two or more, there are two or more R e3 may be the same or different. R e4 is a hydrogen atom or an alkyl group, and is preferably a hydrogen atom in view of ease of producing the compound. e4 If there are two or more, there are two or more R e4 may be the same or different. e4 If there are two or more, there are two or more R e4 may be the same or different. R e5 is a hydrogen atom or a halogen atom, and is preferably a hydrogen atom in view of ease of producing the compound.

[0056] d1 is 0 or 1. d2 is an integer of 0 to 3, preferably 1 or 2. d1+d2 is an integer of 1 to 3. d3 is 0 or 1. d4 is an integer of 0 to 3, preferably 2 or 3. d3+d4 is an integer of 1 to 3. d1+d3 is 1. d2+d4 is Y 11 is an integer of 1 to 5, preferably 4 or 5, and Y 21 and Y 22 is an integer of 1 to 5, preferably an integer of 3 to 5, and particularly preferably 4 or 5. e1+e2 is 3 or 4. e1 is Y 11 is 1 in Y21 and Y 22 e2 is 1 in Y 11 is 1 to 3, preferably 2 or 3, and Y 21 and Y 22 In the formula, the number is 1 to 3, and 2 or 3 is preferred. h1 is Y 11 is 1 in Y 21 and Y 22 h2 is 1 in Y 11 is an integer of 1 or more (preferably 2 or 3), and Y 21 and Y 22 is an integer of 1 or more (preferably 2 or 3). i1+i2 is Y 11 is 2 to 4 (preferably 3 or 4), and Y 21 and Y 22 is an integer of 2 to 4 (preferably 3 or 4). 11 is 1 in Y 21 and Y 22 In Y 11 is an integer of 1 to 3 (preferably 2 or 3), and Y 21 and Y 22 is an integer of 1 to 3 (preferably 2 or 3). i3 is an integer of 0 to 3, preferably 1 to 3, and particularly preferably 2 or 3. i4 is Y 11 is 1 or more (preferably an integer of 2 to 10, particularly preferably an integer of 2 to 6), and Y 21 and Y 22 is 1 or more (preferably an integer of 1 to 10, particularly preferably an integer of 1 to 6). i5 is Y 11 is 1 or more (preferably an integer of 2 to 7), and Y 21 and Y 22 is 1 or more (preferably an integer of 2 to 7).

[0057] Q 22 , Q 23 , Q 24 , Q25 , Q 26 , Q 27 , Q 28 From the viewpoint of ease of production of Compounds 1-11 and 1-21, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2.

[0058] Z 1 The ring structure in Z includes the ring structures described above, and the preferred embodiments are also the same. 1 The ring structure in 1 YaQ 24 is directly bonded, so that, for example, an alkylene group is connected to the ring structure, and A 1 YaQ 24 are never connected. Z a is an organopolysiloxane residue having a valence of (i5+1), and the following group is preferred: a are each independently an alkyl group (preferably having 1 to 10 carbon atoms) or a phenyl group.

[0059] [ka]

[0060] R e1 , R e2 , R e3 or R e4 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of Compounds 1-11 and 1-21. R e2 The number of carbon atoms in the alkyl group of the acyloxy group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of Compounds 1-11 and 1-21. h1 is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1, from the viewpoint of ease of production of Compound 1-11 and Compound 1-21. h2 is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3, from the viewpoint of ease of production of Compound 1-11 and Compound 1-21.

[0061] Y 11 Other forms of g3-1 include the group g3-1 (where d1+d3=1 (i.e., d1 or d3 is 0), g1=d2×r1+d4×r1), the group g3-2 (where e1=1, g1=e2×r1), the group g3-3 (where g1=2×r1), the group g3-4 (where h1=1, g1=h2×r1), the group g3-5 (where i1=1, g1=i2×r1), the group g3-6 (where g1=r1), the group g3-7 (where g1=r1×(i3+1)), the group g3-8 (where g1=r1×i4), and the group g3-9 (where g1=r1×i5). Y 21 and Y 22 Other forms of the group include a group g3-1 (where g2=d2×r1+d4×r1, k1=d2×r1+d4×r1), a group g3-2 (where g2=e2×r1, k1=e2×r1), a group g3-3 (where g2=2×r1, k1=2×r1), a group g3-4 (where g2=h2×r1, k1=h2×r1), a group g3-5 (where, g2=i2×r1, k1=i2×r1), group g3-6 (where g2=r1, k1=r1), group g3-7 (where g2=r1×(i3+1), k1=r1×(i3+1)), group g3-8 (where g2=r1×i4, k1=r1×i4), and group g3-9 (where g2=r1×i5, k1=r1×i5).

[0062] [ka]

[0063] (-A1 -) e1 C(R e2 ) 4-e1-e2 (-Q 22 -G 1 ) e2 Formula (g3-2) -A 1 -N(-Q 23 -G 1 )2 formula (g3-3) (-A 1 -) h1 Z 1 (-Q 24 -G 1 ) h2 Formula (g3-4) (-A 1 -) i1 Si(R e3 ) 4-i1-i2 (-Q 25 -G 1 ) i2 Formula (g3-5) -A 1 -Q 26 -G 1 Formula (g3-6) -A 1 -CH(-Q 22 -G 1 )-Si(R e3 ) 3-i3 (-Q 25 -G 1 ) i3 Formula (g3-7) -A 1 -[CH2C(R e4 )(-Q 27 -G 1 )] i4 -R e5 Formula (g3-8) -A 1 -Z a (-Q 28 -G 1 ) i5 Formula (g3-9)

[0064] However, in formulas (g3-1) to (g3-9), A 1 (OX) m Connect to the G side 1 connects to the OH side.

[0065] G 1 is a group g3, and in each formula, G 1 If there are two or more, there are two or more G 1 may be the same or different. 1 The symbols other than are the same as those in formulas (g2-1) to (g2-9). -Si(R 8 ) 3-r1 (-Q 3 -) r1 Formula (g3) However, in equation (g3), Si is Q 22 , Q 23 , Q 24 , Q 25 , Q 26 , Q 27 and Q 28 Connect to the Q side 3 connects to the OH side. R 8 is an alkyl group. 3 is an alkylene group or an alkylene group having two or more carbon atoms with -C(O)NR between carbon atoms. 6 -, -C(O)-, -NR 6 - or -O-, and two or more Q 3 may be the same or different. r1 is 2 or 3. R 6 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[0066] Q 3 From the viewpoint of ease of production of Compounds 1-11 and 1-21, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. However, when a specific bond is present between carbon atoms, the lower limit of the number of carbon atoms in the alkylene group is 2. R 8 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2, from the viewpoint of ease of production of Compounds 1-11 and 1-21.

[0067] Z in formula (1) (Y in formula (1-11) 11 , Y in formula (1-21) 21and Y 22 ) is preferably an alkylene group which may have -O- between carbon atoms, or group g2-2. A hydrogen atom of the alkylene group may be substituted with a fluorine atom or a hydroxy group. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6. -OZ-(OH) in formula (1) g A preferred example of the group is -O-(CF2) n4 n4 is an integer of 1 or more, preferably 1 to 6, and particularly preferably 1 to 3.

[0068] Examples of Compound 1-11 and Compound 1-21 include compounds of the following formulae: In the following formulae, a and b each independently represent an integer of 1 or greater, preferably an integer of 1 to 250. c represents an integer of 2 or greater, preferably an integer of 2 to 500. CF3 (OCF2) a (OCF2CF2) b OCF2CH2OH CF3CF2(OCF2) a (OCF2CF2) b OCF2CH2OH CF3CF2CF2(OCF2) a (OCF2CF2) b OCF2CH2OH HOCH2CF2(OCF2) a (OCF2CF2) b OCF2CH2OH CF3CF2CF2(OCF2CF2CF2) c OCF2CF2CH2OH HOCH2CF2CF2(OCF2CF2CF2) a OCF2CF2(OCF2CF2CF2) b OCF2CF2CH2OH HOCH2CF2CF2(OCF2CF2CF2) a OCF2CF2CF2(OCF2CF2CF2) b OCF2CF2CH2OH HOCH2CF2CF2(OCF2CF2CF2)a OCF2CF2CF2CF2(OCF2CF2CF2) b OCF2CF2CH2OH CF3CF2CF2(OCF(CF3)CF2) c OCF(CF3)CH2OH HOCH2CF(CF3)(OCF2CF(CF3)) a OCF2CF2(OCF(CF3)CF2) b OCF(CF3)CH2OH HOCH2CF(CF3)(OCF2CF(CF3)) a OCF2CF2CF2(OCF(CF3)CF2) b OCF(CF3)CH2OH HOCH2CF(CF3)(OCF2CF(CF3)) a OCF2CF2CF2CF2(OCF(CF3)CF2) b OCF(CF3)CH2OH CF3(OCF2CF2OCF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CH2OH CF3CF2(OCF2CF2OCF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CH2OH CF3CF2CF2(OCF2CF2OCF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CH2OH HOCH2CF2OCF2CF2CF2CF2(OCF2CF2OCF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CH2OH HOCH2CF2CF2CF2(OCF2CF2OCF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CH2OH CF3(OCF2CF2OCF2CF2CF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CF2CF2CH2OH CF3CF2(OCF2CF2OCF2CF2CF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CF2CF2CH2OH CF3CF2CF2(OCF2CF2OCF2CF2CF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CF2CF2CF2CH2OH HOCH2CF2OCF2CF2CF2CF2CF2CF2(OCF2CF2OCF2CF2CF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CF2CF2CF2CH2OH HOCH2CF2CF2CF2CF2CF2(OCF2CF2OCF2CF2CF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CF2CF2CF2CH2OH

[0069] The specific compound 1 may be used alone or in combination of two or more kinds. Specific Compound 1 can be produced by a known method.

[0070] In step 1, materials other than those mentioned above may be used. For example, step 1 may be carried out in the presence of a phase transfer catalyst. Specific examples of the phase transfer catalyst include quaternary ammonium salts such as tetrabutylammonium bromide and benzyltriethylammonium chloride.

[0071] <Step 1 Procedure> In step 1, the above-mentioned materials may be mixed all at once, or may be mixed in small amounts in portions. The reaction atmosphere in step 1 may be an inert gas atmosphere or an air atmosphere. The reaction temperature in step 1 is preferably from -40 to 200°C, more preferably from -20 to 100°C, and particularly preferably from 0 to 50°C. The reaction time in step 1 is preferably from 0.01 to 40 hours, more preferably from 0.1 to 24 hours, and particularly preferably from 0.5 to 10 hours.

[0072] The amount of the fluorine-based solvent used is preferably 50 to 500 parts by mass, particularly preferably 100 to 300 parts by mass, per 100 parts by mass of Specific Compound 1, in order to ensure that the reaction in Step 1 proceeds efficiently. The molar amount of the base used is preferably 1.0 to 3.0 times, and particularly preferably 1.3 to 2.0 times, the molar amount of Specific Compound 1 used, in order that the reaction in Step 1 proceeds efficiently. The molar amount of the sulfonylating agent used is preferably 1.0 to 3.0 times, and particularly preferably 1.3 to 2.0 times, the molar amount of Specific Compound 1 used, in order that the reaction in Step 1 proceeds efficiently.

[0073] By carrying out step 1, specific compound 1 is sulfonylated to obtain specific compound 2. Specific Compound 2 has a poly(oxyfluoroalkylene) chain and a sulfonate group. The sulfonate group refers to a group represented by formula (A). -OSO2R Formula (A) In the above formula, R represents an organic group. The organic group is preferably a hydrocarbon group which may have a substituent. Specific examples of the hydrocarbon group which may have a substituent include an alkyl group which may have a substituent and an aryl group which may have a substituent. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 10. Specific examples of the alkyl group include a methyl group, an ethyl group, and a tert-butyl group. The aryl group may have a monocyclic structure or a polycyclic structure. Specific examples of the aryl group include a phenyl group, a naphthyl group, and a biphenyl group. Specific examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, nitro group, nitroso group, cyano group, amino group, hydroxyamino group, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, aralkylamino group having 7 to 12 carbon atoms, diaralkylamino group having 7 to 12 carbon atoms, alkylsulfonylamino group having 1 to 12 carbon atoms, sulfonic acid group, sulfonamide group, azide group, trifluoromethyl group, carboxy Examples of the substituent include an alkyl group, an acyl group having 1 to 12 carbon atoms, an aroyl group having 7 to 12 carbon atoms, a hydroxyl group, an alkyloxy group having 1 to 12 carbon atoms, an aralkyloxy group having 7 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an acyloxy group having 1 to 12 carbon atoms, an aroyloxy group having 7 to 12 carbon atoms, a silyloxy group having 3 to 12 carbon atoms, an alkylsulfonyloxy group having 1 to 12 carbon atoms, and an alkylthio group having 1 to 12 carbon atoms, and the number of substituents can be 0 to 5. Specific examples of the sulfonate group include a tosylate group, a mesylate group, a triflate group, and a nonaflate group.

[0074] [Process 2] Step 2 is a step of contacting the specific product with an adsorbent having a pH of 8.0 or less. By carrying out Step 2, impurities can be removed from the product without decomposing the specific compound 2. Below, first, the materials used in step 2 will be described in detail, and then the procedure for step 2 will be described in detail.

[0075] <Specific adsorbent> The specific adsorbent plays a role in contacting the specific product and adsorbing impurities in the product (for example, residues of the base, residues of the sulfonylating agent, etc.). The pH of the specific adsorbent is 8.0 or less. In particular, a pH of 7.0 or less is preferred in order to further reduce the content of impurities. The lower limit of the pH of the adsorbent is preferably 3.0 or more, more preferably 5.0 or more, in order to facilitate the removal of impurities. The method for measuring the pH of the specific adsorbent is as follows. First, 10 g of the specific adsorbent is added to 100 mL of ion-exchanged water and stirred for 1 hour at 25° C. After that, the mixture is centrifuged and the supernatant is separated and the pH of the supernatant is measured, and the obtained pH is designated as the pH of the specific adsorbent.

[0076] The specific adsorbent is often in the form of particles. The average particle size of the specific adsorbent is preferably from 1 to 500 μm, more preferably from 1 to 350 μm, and even more preferably from 1 to 105 μm, in order to further reduce the content of impurities. The average particle size of the specific adsorbent can be determined by measuring the particle sizes (diameters) of at least 20 specific adsorbents and calculating the arithmetic average. If the specific adsorbent is a commercially available product, the catalog value may be used.

[0077] The specific surface area of ​​the specific adsorbent is 30 to 900 m, which reduces the content of impurities. 2 / g is preferred, and 200 to 800m 2 / g is more preferable, and 600 to 800m 2 / g is particularly preferred. The specific surface area of ​​the specific adsorbent is determined in accordance with the specific surface area measurement method specified in JIS Z 8830 (2013). If the specific adsorbent is a commercially available product, the catalog value may be used.

[0078] The water content of the specific adsorbent is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, in terms of achieving a high yield of the sulfonylated specific compound 1. There is no particular lower limit, but it is often 0.1% by mass or more. The moisture content of the adsorbent is the mass ratio of water to the total mass of the adsorbent, and can be measured by a loss on drying method or the like.

[0079] Specific examples of the specific adsorbent include silica, aluminum hydroxide, hydrotalcite, magnesium silicate, aluminum silicate, aluminum oxide, magnesium oxide, and aluminum oxide-magnesium oxide solid solution, which may be used alone or in combination of two or more.

[0080] <Step 2 Procedure> In step 2, the specific product is brought into contact with the specific adsorbent. Examples of the contacting method include a method of mixing the specific product with the specific adsorbent, and a method of passing the specific product through a filter filled with the specific adsorbent. When the specific product is brought into contact with the specific adsorbent, the specific product may be brought into direct contact with the specific adsorbent, or a solution may be prepared by dissolving or dispersing the specific product in a solvent, and the resulting solution may be brought into contact with the specific adsorbent. The solvent to be used may be any solvent capable of dissolving or dispersing the specific product, and is preferably an organic solvent, more preferably a fluorine-containing solvent, specific examples of which are as described above.

[0081] When the specific product is brought into contact with the specific adsorbent, the amount of the specific adsorbent used is preferably 1 to 200 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the specific compound 1.

[0082] The contact time is preferably from 0.1 to 180 minutes, particularly preferably from 1 to 60 minutes, in that the content of impurities can be further reduced. The temperature during contact is preferably 0 to 40°C, particularly preferably 10 to 30°C, in that the content of impurities can be further reduced.

[0083] It is also preferable not to subject the specific product to a water washing treatment between the end of step 1 and the end of step 2. If the specific product is subjected to a water washing treatment, there is a risk that the specific compound 2 in the specific product may be decomposed, resulting in a decrease in yield. The water-washing treatment refers to a treatment in which the specific product is brought into contact with an aqueous solution. The aqueous solution used in the water-washing treatment may contain salts or the like. Furthermore, step 1 and step 2 do not have to be carried out consecutively. That is, step 2 may be carried out immediately after step 1, or step 2 may be carried out after several steps have been carried out following step 1. In the latter case, for example, step 2 may be carried out after obtaining specific compound 2 and producing a fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group. Alternatively, for example, step 2 may be carried out after obtaining specific compound 2 and producing a fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a group (e.g., an allyl group) to which a reactive silyl group can be introduced, thereby introducing the reactive silyl group and producing a fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group.

[0084] A second embodiment of the production method of the present invention includes step 1 of sulfonylating specific compound 1 in the presence of a fluorine-based solvent, a base, and a sulfonylating agent to obtain a specific product; step 3 of separating the specific product into two phases and separating and recovering the phase having a higher content of specific compound 2; and step 4 of contacting the separated and recovered phase with an adsorbent having a pH of 8.0 or less. By carrying out step 3, the yield of the fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group is improved.

[0085] The procedure of step 1 of the second embodiment is the same as the procedure of step 1 of the first embodiment, and therefore a description thereof will be omitted.

[0086] In step 3, the specific product may be allowed to stand as a method for separating the specific product into two phases. The temperature during standing is preferably 0 to 50°C. Next, of the specific product separated into two phases, the phase having a higher content of specific compound 2 is recovered. For example, if the phase having a higher content of specific compound 2 is the lower phase, only the lower phase is recovered.

[0087] The procedure of step 4 is the same as that of step 2 above, except that the phase separated and recovered in step 3 is used instead of the specific product, and therefore a description thereof will be omitted.

[0088] It is also preferable not to subject the specific product to a water washing treatment between the end of step 1 and the end of step 4. If the specific product is subjected to a water washing treatment, there is a risk that the specific compound 2 in the specific product may be decomposed, resulting in a decrease in yield. The water-washing treatment refers to a treatment in which the specific product is brought into contact with an aqueous solution. The aqueous solution used in the water-washing treatment may contain salts or the like.

[0089] As the specific compound 2 produced by the production method of the present invention (first and second embodiments), compound 2 is preferred. Formula (2) A 1 -(OX) m -OZ-(OSO2R) g X, Z, m, and g in formula (2) are defined the same as X, Z, m, and g in formula (1), respectively. R in formula (2) has the same definition as R in formula (A). A 1 is a perfluoroalkyl group or -Q-(OSOR) k is. The definition of the perfluoroalkyl group is the same as that of the perfluoroalkyl group A in formula (1). Q and k are the same as those defined for Q and k in formula (1). As Compound 2, Compound 2-11 and Compound 2-21 are also preferred. A-(OX) m -OY 11 -(OSO2R) g1 Formula (2-11) (RSO2O) k1 Y 22 -(OX) m -OY 21 -(OSO2R) g2 Formula (2-21) A, X, and Y in formula (2-11) 11 , m, and g1 are A, X, and Y in formula (1-11), respectively. 11 , m and g1 are defined as follows: R in formula (2-11) has the same definition as R in formula (A). Y in formula (2-21) 22 , X, Y 21 , k1, m, and g2 are the Y 22 , X, Y 21 , k1, m and g2 are synonymous with the definitions. R in formula (2-21) has the same definition as R in formula (A).

[0090] The fluorine-containing ether compounds having a poly(oxyfluoroalkylene) chain and a sulfonate group produced by the above-mentioned production methods (first and second embodiments) of the present invention are useful as intermediates for producing fluorine-containing ether compounds having a poly(oxyfluoroalkylene) chain and a reactive silyl group. For example, a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a reactive silyl group can be produced using the sulfonated specific compound 1 produced according to the method described in Patent Document 1. [Example]

[0091] The present invention will be described in detail below with reference to examples. Examples 1 to 9 and 15 to 19 are working examples, and Examples 10 to 14 are comparative examples. However, the present invention is not limited to these examples. The blending amounts of each component in the tables below are based on mass.

[0092] The adsorbents used in Examples 1 to 14 are as follows. Silica gel D-75-60A(N) (AGC Si-Tech Co., Ltd., average particle size: 72 μm, specific surface area: 751 m 2 / g, moisture content: 6.9% by mass) Silica gel D-75-60A (AGC Si-Tech Co., Ltd., average particle size: 74 μm, specific surface area: 709 m 2 / g, moisture content: 6.7% by mass) Kyoward 200 (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 318 μm, specific surface area: 211 m 2 / g, moisture content: 18.8% by mass) Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 261 μm, specific surface area: 206 m 2 / g, moisture content: 15.6% by mass) Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 273 μm, specific surface area: 201 m 2 / g, moisture content: 3.3% by mass) KW-2000 (Kyowa Chemical Industry Co., Ltd., average particle size: 48 μm, specific surface area: 190 m 2 / g, moisture content: 14.9% by mass) Alumina (Fujifilm Wako Pure Chemical Industries, Ltd., average particle size: 126 μm, specific surface area: 539 m 2 / g, moisture content: 7.8% by mass)

[0093] [Example 1] A 200 mL glass recovery flask was charged with 50.0 g of specific compound 1 (compound (1-1)), 50.1 g of AE-3000, 1.63 g of 2,6-dimethylpyridine (2,6-lutidine), and 4.25 g of trifluoromethanesulfonic anhydride. The mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. After the reaction was complete, the mixture was allowed to stand and separated into two phases. The lower phase was collected. The collected lower phase was filtered through 25.0 g of silica gel D-75-60A(N) and washed with 150 g of AE-3000. The AE-3000 was distilled off from the mixture, yielding 49.8 g of a product containing compound (2-1) (93% recovery, 99.9% purity). CF3-O-(CF2CF2OCF2CF2CF2CF2O) x -CF2CF2OCF2CF2CF2CH2-OH (1-1) CF3-O-(CF2CF2OCF2CF2CF2CF2O) x -CF2CF2OCF2CF2CF2CH2-OSO2CF3...(2-1) x represents the repeat number, and the repeat number of the compound used in this example was 14.0.

[0094] [Examples 2-5, Examples 10-13] A product containing compound (2-1) was obtained by the same procedure as in Example 1, except that the adsorbents and fluorinated solvents listed in Tables 1 and 2 were used instead of silica gel D-75-60A(N).

[0095] [Example 6] The mixture was filtered through silica gel D-75-60A(N) without being allowed to stand for two-phase separation, and a product containing compound (2-1) was obtained in the same manner as in Example 1, except that the amount of adsorbent used was changed as shown in Table 1.

[0096] [Examples 7-9] A product containing compound (2-1) was obtained in the same manner as in Example 6, except that the adsorbent shown in Table 1 was used instead of silica gel D-75-60A(N) and the amount of adsorbent used was changed as shown in Table 1.

[0097] [Example 14] In a 200 mL glass recovery flask, 50.0 g of specific compound 1 (compound (1-1)), 50.1 g of 1,3-bis(trifluoromethyl)benzene, 1.63 g of triethylamine, and 4.25 g of trifluoromethanesulfonic anhydride were placed, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. The resulting mixture was washed with water, and the organic phase was recovered. 1,3-bis(trifluoromethyl)benzene was distilled off from the recovered organic phase, yielding a product containing compound (2-1).

[0098] [Example 15] In a 200 mL glass recovery flask, 50.0 g of specific compound 1 (compound (1-2), 50.0 g of AE-3000, 1.64 g of 2,6-dimethylpyridine (2,6-lutidine), and 4.25 g of trifluoromethanesulfonic anhydride were placed, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. After the reaction was completed, a product containing compound (2-2) was obtained by following the same procedure as in Example 1, except that silica gel D-75-60A was used instead of silica gel D-75-60A(N). CF3 (OCF2) a (OCF2CF2) bOCF2CH2-OH (1-2) CF3 (OCF2) a (OCF2CF2) b OCF2CH2-OSO2CF3···(2-2) The numbers a and b represent the repeating numbers, and the repeating numbers of the compound used in this example were a = 28.0 and b = 17.0. The order in which (OCF2) and (OCF2CF2) are present is arbitrary.

[0099] [Example 16] In a 200 mL glass recovery flask, 50.0 g of compound (1-3), which is specific compound 1, 50.0 g of AE-3000, 3.27 g of 2,6-dimethylpyridine (2,6-lutidine), and 8.50 g of trifluoromethanesulfonic anhydride were placed, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. After completion of the reaction, a product containing compound (2-3) was obtained according to the same procedure as in Example 15. HOCH2CF2(OCF2) a (OCF2CF2) b OCF2CH2-OH (1-3) CF3SO2O-CH2CF2(OCF2) a (OCF2CF2) b OCF2CH2-OSO2CF3···(2-3) The numbers a and b represent the repeating numbers, and the repeating numbers of the compound used in this example were a = 28.0 and b = 17.0. The order in which (OCF2) and (OCF2CF2) are present is arbitrary.

[0100] [Example 17] In a 200 mL glass recovery flask, 50.0 g of compound (1-4), which is specific compound 1, 50.1 g of AE-3000, 1.64 g of 2,6-dimethylpyridine (2,6-lutidine), and 4.25 g of trifluoromethanesulfonic anhydride were placed, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. After completion of the reaction, a product containing compound (2-4) was obtained according to the same procedure as in Example 15. CF3CF2CF2(OCF(CF3)CF2) cOCF(CF3)CH2-OH (1-4) CF3CF2CF2(OCF(CF3)CF2) c OCF(CF3)CH2-OSO2CF3...(2-4) c represents the repeat number, and the repeat number of the compound used in this example was 28.0.

[0101] [Example 18] In a 200 mL glass recovery flask, 50.0 g of compound (1-5), which is specific compound 1, 50.0 g of AE-3000, 1.63 g of 2,6-dimethylpyridine (2,6-lutidine), and 4.26 g of trifluoromethanesulfonic anhydride were placed, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. After completion of the reaction, a product containing compound (2-5) was obtained according to the same procedure as in Example 15. CF3CF2CF2(OCF2CF2CF2) c OCF2CF2CH2-OH (1-5) CF3CF2CF2(OCF2CF2CF2) c OCF2CF2CH2-OSO2CF3···(2-5) c represents the repeat number, and the repeat number of the compound used in this example was 30.0.

[0102] [Example 19] In a 200 mL glass recovery flask, 50.0 g of compound (1-6), which is specific compound 1, 50.0 g of AE-3000, 3.26 g of 2,6-dimethylpyridine (2,6-lutidine), and 8.52 g of trifluoromethanesulfonic anhydride were placed, and the mixture was stirred at room temperature under a nitrogen atmosphere for 1 hour. After completion of the reaction, a product containing compound (2-6) was obtained according to the same procedure as in Example 15. HOCH2CF2CF2CF2(OCF2CF2OCF2CF2CF2CF2) a OCF2CF2OCF2CF2CF2CH2-OH (1-6) CF3SO2O-CH2CF2CF2CF2(OCF2CF2OCF2CF2CF2CF2) aOCF2CF2OCF2CF2CF2CH2-OSO2CF3...(2-6) a represents the repeat number, and the repeat number of the compound used in this example was 10.0.

[0103] In Tables 1 to 3, the "Step 3" column indicates that the above-mentioned step 3 was performed, with "◯" and that it was not performed, with "×". In Tables 1 to 3, the column "Washing after reaction" indicates "No" if the product obtained in step 1 was not washed with water between the end of step 1 and the end of step 2 or between the end of step 1 and the end of step 4, and indicates "Yes" if the product was washed with water. In Tables 1 to 3, "adsorbent pH" represents the pH of the adsorbent. The method for measuring the pH of the specific adsorbent is as described above. In Tables 1 to 3, "amount of adsorbent" represents the ratio of the amount of adsorbent used to the amount of specific compound 1 used as the raw material (amount of adsorbent used (wt) / amount of specific compound 1 used (wt)).

[0104] In Tables 1 to 3, the column "recovery rate" indicates the ratio (%) of the molar amount of the obtained specific compound 2 to the charged amount (molar amount) of the specific compound 1 as a raw material. In Tables 1 to 3, the column "Decomposition of target product" indicates the decomposition rate of specific compound 1 in the obtained product [{molar amount of specific compound 2 / (molar amount of specific compound 2+molar amount of undecomposed specific compound 2)}×100], where "◎" indicates a decomposition rate of 0%, "○" indicates a decomposition rate of more than 0% and not more than 0.1%, "△" indicates a decomposition rate of more than 0.1% and not more than 0.5%, and "×" indicates a decomposition rate of more than 0.5%. In Tables 1 to 3, the "Impurity Remaining Amount" column indicates the impurity remaining rate of impurities other than specific compound 1 in the obtained product, expressed as {(molar amount of impurity / molar amount of product) × 100}, where "◎" indicates an impurity remaining rate of 0%, "○" indicates an impurity remaining rate of more than 0% and 0.1% or less, "△" indicates an impurity remaining rate of more than 0.1% and 0.5% or less, and "×" indicates an impurity remaining rate of more than 0.5%.

[0105] [Table 1]

[0106] [Table 2]

[0107] [Table 3]

[0108] As shown in Tables 1, 2 and 3, it was confirmed that the desired effects were obtained according to the manufacturing method of the present invention. In particular, when the pH of the adsorbent is 7.0 or less, as in Examples 2, 7 and 15 to 19, it was confirmed that the effect was even more excellent.

[0109] The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2020-155282, filed on September 16, 2020, are hereby incorporated by reference as part of the disclosure of the specification of the present invention.

Claims

1. Step 1: sulfonylating a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group in the presence of a fluorine-containing solvent, a base, and a sulfonylating agent to obtain a product containing a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group; and step 2 of contacting the product obtained in step 1 with an adsorbent having a pH of 3.0 or more and 8.0 or less, The adsorbent is granular, The specific surface area of ​​the adsorbent is 30 to 900 m ２ / g, the adsorbent is at least one selected from the group consisting of silica, aluminum hydroxide, hydrotalcite, magnesium silicate, aluminum silicate, aluminum oxide, magnesium oxide, and an aluminum oxide-magnesium oxide solid solution; The method for producing a fluorinated ether compound, wherein the amount of the adsorbent used is 1 to 100 parts by mass per 100 parts by mass of the fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group.

2. 2. The method for producing a fluorinated ether compound according to claim 1, wherein the product obtained in step 1 is not subjected to a water washing treatment during the period from the end of step 1 to the end of step 2.

3. Step 1: sulfonylating a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group in the presence of a fluorine-containing solvent, a base, and a sulfonylating agent to obtain a product containing a fluorine-containing ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group; a step 3 of separating the product obtained in the step 1 into two phases and separating and recovering the phase having a higher content of the fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a sulfonate group; and step 4 of contacting the separated and recovered phase with an adsorbent having a pH of 3.0 or more and 8.0 or less; The adsorbent is granular, The specific surface area of ​​the adsorbent is 30 to 900 m ２ / g, the adsorbent is at least one selected from the group consisting of silica, aluminum hydroxide, hydrotalcite, magnesium silicate, aluminum silicate, aluminum oxide, magnesium oxide, and an aluminum oxide-magnesium oxide solid solution; The method for producing a fluorinated ether compound, wherein the amount of the adsorbent used is 1 to 100 parts by mass per 100 parts by mass of the fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group.

4. 4. The method for producing a fluorinated ether compound according to claim 3, wherein the product obtained in step 1 is not subjected to a water washing treatment during the period from the end of step 1 to the end of step 4.

5. The method for producing a fluorinated ether compound according to any one of claims 1 to 4, wherein the adsorbent has a pH of 7.0 or less.

6. The method for producing a fluorinated ether compound according to any one of claims 1 to 5, wherein the adsorbent has an average particle size of 1 to 500 µm.

7. The method for producing a fluorinated ether compound according to any one of claims 1 to 6, wherein the adsorbent has a water content of 30 mass% or less.

8. The method for producing a fluorinated ether compound according to any one of claims 1 to 7, wherein the fluorinated ether compound having a poly(oxyfluoroalkylene) chain and a hydroxyl group is a compound represented by formula (1): Formula (1) A-(OX) ｍ -O-Z-(OH) ｇ A is a perfluoroalkyl group or -Q-(OH) ｋ and Z is a (g+1)-valent linking group, X is a fluoroalkylene group having one or more fluorine atoms, m is an integer of 2 or greater; g is an integer of 1 or greater; Q is a (k+1)-valent linking group, k is an integer of 1 or more.

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